CN102939319B - Precise control of molecular weight and chain shape in carbon dioxide/epoxide alternating copolymerization and preparation of low-molecular-weight poly(alkylene carbonate) thereby - Google Patents
Precise control of molecular weight and chain shape in carbon dioxide/epoxide alternating copolymerization and preparation of low-molecular-weight poly(alkylene carbonate) thereby Download PDFInfo
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- CN102939319B CN102939319B CN201080067235.2A CN201080067235A CN102939319B CN 102939319 B CN102939319 B CN 102939319B CN 201080067235 A CN201080067235 A CN 201080067235A CN 102939319 B CN102939319 B CN 102939319B
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- -1 poly(alkylene carbonate Chemical compound 0.000 title claims abstract description 83
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 238000012648 alternating copolymerization Methods 0.000 title claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 title abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 title abstract description 11
- 150000002118 epoxides Chemical class 0.000 title description 31
- 238000002360 preparation method Methods 0.000 title description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 40
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 64
- 229910052698 phosphorus Inorganic materials 0.000 claims description 62
- 239000002253 acid Substances 0.000 claims description 46
- 235000011089 carbon dioxide Nutrition 0.000 claims description 45
- 229910052736 halogen Inorganic materials 0.000 claims description 43
- 150000002367 halogens Chemical class 0.000 claims description 43
- 150000002500 ions Chemical class 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims description 36
- 125000004437 phosphorous atom Chemical group 0.000 claims description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 33
- 125000005843 halogen group Chemical group 0.000 claims description 33
- 229910052760 oxygen Inorganic materials 0.000 claims description 33
- 239000001301 oxygen Substances 0.000 claims description 33
- 229910052710 silicon Inorganic materials 0.000 claims description 31
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 29
- 239000010703 silicon Substances 0.000 claims description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 28
- 239000005864 Sulphur Substances 0.000 claims description 28
- 239000011574 phosphorus Substances 0.000 claims description 28
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 125000003545 alkoxy group Chemical group 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 19
- 125000004185 ester group Chemical group 0.000 claims description 18
- 150000003254 radicals Chemical class 0.000 claims description 18
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 17
- 125000006743 (C1-C60) alkyl group Chemical group 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 14
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 14
- 125000004104 aryloxy group Chemical group 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 10
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 9
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000002861 polymer material Substances 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 150000002466 imines Chemical class 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 229910052752 metalloid Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 229960001866 silicon dioxide Drugs 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 125000003282 alkyl amino group Chemical group 0.000 claims description 6
- 125000005910 alkyl carbonate group Chemical group 0.000 claims description 6
- 125000001769 aryl amino group Chemical group 0.000 claims description 6
- 230000005595 deprotonation Effects 0.000 claims description 6
- 238000010537 deprotonation reaction Methods 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 125000003158 alcohol group Chemical group 0.000 claims description 5
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 5
- CFHIDWOYWUOIHU-UHFFFAOYSA-N oxomethyl Chemical compound O=[CH] CFHIDWOYWUOIHU-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 3
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 150000001261 hydroxy acids Chemical group 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 72
- 239000012986 chain transfer agent Substances 0.000 abstract description 66
- 239000003054 catalyst Substances 0.000 abstract description 45
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 20
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract description 3
- 239000012948 isocyanate Substances 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 71
- 239000004793 Polystyrene Substances 0.000 description 39
- 229920002223 polystyrene Polymers 0.000 description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 34
- 238000007334 copolymerization reaction Methods 0.000 description 33
- 238000009826 distribution Methods 0.000 description 26
- 238000005259 measurement Methods 0.000 description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 18
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 17
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 16
- 239000002585 base Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 229920005603 alternating copolymer Polymers 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920000379 polypropylene carbonate Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 230000007306 turnover Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 230000037452 priming Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 244000309464 bull Species 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 3
- 235000021286 stilbenes Nutrition 0.000 description 3
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- NHYCGSASNAIGLD-UHFFFAOYSA-N Chlorine monoxide Chemical compound Cl[O] NHYCGSASNAIGLD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010669 acid-base reaction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 description 2
- 239000011243 crosslinked material Substances 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
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- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- CCEFMUBVSUDRLG-KXUCPTDWSA-N (4R)-limonene 1,2-epoxide Natural products C1[C@H](C(=C)C)CC[C@@]2(C)O[C@H]21 CCEFMUBVSUDRLG-KXUCPTDWSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RITWYHYBNAHXSR-UHFFFAOYSA-N 1,2-dioxacycloundecane Chemical compound C1CCCCOOCCCC1 RITWYHYBNAHXSR-UHFFFAOYSA-N 0.000 description 1
- WEEGYLXZBRQIMU-UHFFFAOYSA-N 1,8-cineole Natural products C1CC2CCC1(C)OC2(C)C WEEGYLXZBRQIMU-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- CBDLNOVOFXJEOB-UHFFFAOYSA-N 1-methoxy-4-(4-methoxyphenoxy)benzene Chemical compound C1=CC(OC)=CC=C1OC1=CC=C(OC)C=C1 CBDLNOVOFXJEOB-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- UFBJCMHMOXMLKC-UHFFFAOYSA-M 2,4-dinitrophenol(1-) Chemical compound [O-]C1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-M 0.000 description 1
- OSPYYCFTJINYEV-UHFFFAOYSA-N 2-(2-phenoxyethyl)oxirane Chemical compound C=1C=CC=CC=1OCCC1CO1 OSPYYCFTJINYEV-UHFFFAOYSA-N 0.000 description 1
- OIFAHDAXIUURLN-UHFFFAOYSA-N 2-(fluoromethyl)oxirane Chemical compound FCC1CO1 OIFAHDAXIUURLN-UHFFFAOYSA-N 0.000 description 1
- PQWKLUKTIZEJHB-UHFFFAOYSA-N 2-(hexan-2-yloxymethyl)oxirane Chemical group CCCCC(C)OCC1CO1 PQWKLUKTIZEJHB-UHFFFAOYSA-N 0.000 description 1
- QYYCPWLLBSSFBW-UHFFFAOYSA-N 2-(naphthalen-1-yloxymethyl)oxirane Chemical compound C=1C=CC2=CC=CC=C2C=1OCC1CO1 QYYCPWLLBSSFBW-UHFFFAOYSA-N 0.000 description 1
- LSWYGACWGAICNM-UHFFFAOYSA-N 2-(prop-2-enoxymethyl)oxirane Chemical group C=CCOCC1CO1 LSWYGACWGAICNM-UHFFFAOYSA-N 0.000 description 1
- NWLUZGJDEZBBRH-UHFFFAOYSA-N 2-(propan-2-yloxymethyl)oxirane Chemical compound CC(C)OCC1CO1 NWLUZGJDEZBBRH-UHFFFAOYSA-N 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- JFDMLXYWGLECEY-UHFFFAOYSA-N 2-benzyloxirane Chemical compound C=1C=CC=CC=1CC1CO1 JFDMLXYWGLECEY-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 description 1
- UKTHULMXFLCNAV-UHFFFAOYSA-N 2-hex-5-enyloxirane Chemical compound C=CCCCCC1CO1 UKTHULMXFLCNAV-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical group C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- CCEFMUBVSUDRLG-XNWIYYODSA-N Limonene-1,2-epoxide Chemical compound C1[C@H](C(=C)C)CCC2(C)OC21 CCEFMUBVSUDRLG-XNWIYYODSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- GNKTZDSRQHMHLZ-UHFFFAOYSA-N [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] Chemical compound [Si].[Si].[Si].[Ti].[Ti].[Ti].[Ti].[Ti] GNKTZDSRQHMHLZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- JATDUNZBQNXKGY-UHFFFAOYSA-N benzene-1,2,4-tricarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1.OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 JATDUNZBQNXKGY-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical group C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohexene oxide Chemical group O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- DFBKLUNHFCTMDC-PICURKEMSA-N dieldrin Chemical compound C([C@H]1[C@H]2[C@@]3(Cl)C(Cl)=C([C@]([C@H]22)(Cl)C3(Cl)Cl)Cl)[C@H]2[C@@H]2[C@H]1O2 DFBKLUNHFCTMDC-PICURKEMSA-N 0.000 description 1
- 229950006824 dieldrin Drugs 0.000 description 1
- NGPMUTDCEIKKFM-UHFFFAOYSA-N dieldrin Natural products CC1=C(Cl)C2(Cl)C3C4CC(C5OC45)C3C1(Cl)C2(Cl)Cl NGPMUTDCEIKKFM-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CJXOCUBZVDKUCO-UHFFFAOYSA-N ethoxymethoxymethylbenzene Chemical compound CCOCOCC1=CC=CC=C1 CJXOCUBZVDKUCO-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- QTBFPMKWQKYFLR-UHFFFAOYSA-N isobutyl chloride Chemical compound CC(C)CCl QTBFPMKWQKYFLR-UHFFFAOYSA-N 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- UCAOGXRUJFKQAP-UHFFFAOYSA-N n,n-dimethyl-5-nitropyridin-2-amine Chemical compound CN(C)C1=CC=C([N+]([O-])=O)C=N1 UCAOGXRUJFKQAP-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N n-alpha-hexadecene Natural products CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229940095068 tetradecene Drugs 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/06—Cobalt compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
- C08G64/0216—Aliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/40—Post-polymerisation treatment
- C08G64/406—Purifying; Drying
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
This invention relates to a method of preparing poly(alkylene carbonate) that has a molecular weight and polymer chain structure precisely controlled by adding a chain transfer agent composed of a compound having an alcohol or carboxylic acid functional group upon alternating copolymerization of an epoxide compound and carbon dioxide using a catalyst composed of a trivalent metal complex compound synthesized from a quaternary ammonium salt-containing Salen type ligand, and to a polymer compound prepared thereby. According to this invention, the polymer compound having a star-shaped chain as well as the polymer having a linear chain can be prepared. The low-molecular-weight poly(alkylene carbonate) has an -OH terminal group and can be used alone as a coating agent, etc., and also in mixtures with an isocyanate compound and thus can be easily utilized to prepare polyurethane.
Description
Technical field
The present invention relates to a kind of when using the catalyzer comprising the trivalent metal complex compound synthesized by the Salen type part containing quaternary ammonium salt to be prepared the process of the alternating copolymer of carbonic acid gas and epoxide, the compound with alcohol or carboxylic acid functional is used accurately to control the molecular weight of polymkeric substance and the method for Similarity Between Line Segments as chain-transfer agent, and the lower molecular weight prepared thus poly-(alkylene carbonates).
Background technology
Poly-(alkylene carbonates) is easy biodegradable polymkeric substance, and can be used as the illustrative examples of packaging or coating material.It is very eco-friendly for preparing poly-(alkylene carbonates) by epoxy compounds and carbonic acid gas, because do not use poisonous phosgene, and carbonic acid gas can obtain at an easy rate.
Since twentieth century sixties, many researchists have developed many kinds for the catalyzer by epoxy compounds and carbon dioxide production poly-(alkylene carbonates).Recently, the present inventor has disclosed a kind of by the Salen [H containing quaternary ammonium salt
2salen=N, N '-bis-(3,5-dialkyl group salicylidene)-ethylene diamines] type part synthesis catalyzer [Bun-Yeoul Lee, the Korean patent No. 10-0853358 (date of issue: 2008.08.13) with high reactivity and highly selective; Bun-Yeoul Lee, Sujith S, Eun-Kyung Noh, Jae-Ki Min, Korean Patent Application No. 10-2008-0015454 (Date to Tender Notice of Readiness: 2008.02.20); Bun-Yeoul Lee, Sujith S, Eun-Kyung Noh, Jae-Ki Min, PCT/KR2008/002453 (Date to Tender Notice of Readiness: 2008.04.30); Eun-Kyung Noh, Sung-Jae Na, Sujith S, Sang-Wook Kim, and Bun-Yeoul Lee J.Am.Chem.Soc.2007,129,8082-8083 (2007.07.04); Sujith S, Jae-Ki Min, Jong-Eon Seong, Sung-Jae Na, and Bun-Yeoul Lee, Angew.Chem.Int.Ed., 2008,47,7306-7309 (2008.09.08)].Catalyzer disclosed in the present inventor is high activity and highly selective, and the preparation of the multipolymer with high molecular and polymerization can be made even at high temperature also can to carry out, and is applicable to the process of commercially producing thus.In addition, there is advantage in this catalyzer, because comprise quaternary ammonium salt in part, catalyzer can easily be separated with the multipolymer obtained by carbonic acid gas and epoxide thus, and is used again.
In addition, the present inventor is carefully verified has greater activity and the catalyzer compared with highly selective in the catalyst group of above-mentioned patent, thus verified this catalyzer has unique texture, the non-coordination of the nitrogen-atoms of Salen part in this unique texture, and only have Sauerstoffatom and metal-complexing, this is not yet known (see following structure 1 so far, Sung-Jae Na, Sujith S, Anish Cyriac, Bo-Eun Kim, Jina Yoo, Youn K.Kang, Su-Jung Han, Chongmok Lee, and Bun-Yeoul Lee " Elucidation of the Structure of AHighly Active Catalytic System for CO
2/ Epoxide Copolymerization:A Salen-CobaltateComplex of An Unusual Binding Mode " Inorg.Chem.2009,48,10455 – 10465).
2,4-dinitrophenolate=2,4-nitro phenates
In addition, easily the method for the part of the compound of composite structure 1 has also obtained developing (Min, J.; Seong, J.E.; Na, S.J.; Cyriac, A.; Lee, B.Y.Bull.Korean Chem.Soc.2009,30,745-748).
High-molecular-weight poly (alkylene carbonates) can use the compound of structure 1 to prepare economically as high activated catalyst.But, due to poly-(alkylene carbonates), there is lower glass transition temperatures (being 40 DEG C in the situation of poly-(alkylene carbonates) prepared by propylene oxide and carbonic acid gas) and there is insufficient physical strength, therefore to being applied with predetermined restriction by the application of its exploitation.
For overcoming these limitations of poly-(alkylene carbonates), developing preparation and there is poly-(alkylene carbonates) polyvalent alcohol of lower molecular weight and multiple-OH end group and prepared the method for urethane by it.Urethane is that compound by making to have-OH group reacts with the compound with isocyanic ester (-NCO) group thus forms the polymkeric substance that amino-formate bond (-NHC (O) O-) obtains.Developing many kinds to have the-compound of NCO group and there is the compound of-OH group, and developing and used the thermoplasticity or thermosetting resin or elastic polyurethane with various character.2007, urethane was with the amount of about 1,200 ten thousand tons preparation and use in worldwide, and its amount is annual afterwards improves 5%, and its application has become more extensive.The example with the compound of-OH group comprises the glycol and polyester glycol with-OH end group, and they have ring-opening polymerization by ethylene oxide or propylene oxide and the thousands of molecular weight obtained.Poly-(alkylene carbonates) glycol replacing poly-(alkylene oxide) glycol or polyester glycol to use for preparation plan or polyvalent alcohol are to obtain urethane; carry out attempting (W.Kuran; in:Polymeric MaterialsEncyclopedia; J.C.Salamone; Ed.CRC Press, Inc., Boca Raton 1996; Vol.9, p.6623; Polymer, 1992, vol 33,1384).Compared with the known ammonia ester with being prepared by polyester polyol of urethane prepared by poly-(alkylene carbonates) polyvalent alcohol, there is higher water-disintegrable (EP 302712; USP 5863627), and be in the news there is higher antistatic property (USP 4931486).In addition, it is reported antithrombotic compendency also very high (WO9857671).
EP 302712 (right of priority Date to Tender Notice of Readiness: 1987.08.04) and EP 311278 (right of priority Date to Tender Notice of Readiness: 1987.10.06) discloses by by diethyl carbonate (EtOC (O) OEt) and 1,6-hexylene glycol or the polycondensation of 1,6-pentanediol and the Copolycarbonate glycol prepared and prepare urethane by it.In addition, USP 5171830 (Date to Tender Notice of Readiness: 1991.08.16) discloses and passes through dialkyl carbonate (ROC (O) OR) and the α with more than 4 carbon under alkaline catalysts exists, ω-alkane glycol polycondensation and synthesize the method for poly-(alkylene carbonates), and use the method to prepare ammonia ester resin.
EP 798328A2 (right of priority Date to Tender Notice of Readiness: 1996.03.28) discloses and utilizes the polycondensation of polyether glycol and methylcarbonate (MeOC (O) OMe) to carry out polycarbonate synthesis copolyether glycol.
In addition, utilize the polycondensation of various glycol and carbonic acid ethylidene ester to synthesize poly-(alkylene carbonates) macromolecular diol and to utilize this synthesis to be disclosed in Journal of Applied Polymer Science 1998 to prepare urethane, 69,1621 – 1633 and Journal ofApplied Polymer Science, 1989, in 37,1491 – 1511.
But described poly-(alkylene carbonates) polyvalent alcohol does not utilize the copolymerization of carbonic acid gas and epoxide and prepares, and has the structure of the multipolymer being different from carbonic acid gas and epoxide.Specifically, for utilizing the polycondensation of carbonic acid ethylidene ester or dialkyl carbonate to prepare poly-(alkylene carbonates), the glycol every more than 3 carbon should be used.That is, carbonic acid ester bond has the structure connected by more than 3 carbon.Poly-(alkylene carbonates) that obtained by carbonic acid gas and the copolymerization of epoxide is constructed to carbonic acid ester bond is connected by 2 carbon.
USP 4686276 (Date to Tender Notice of Readiness: 1985.12.30) discloses a kind of method by using catalyzer and initiator carbonic acid gas and ethylene oxide copolymerization to be synthesized poly-(carbonic acid ethylidene ester) glycol under the presence or absence of carbonic acid ethylidene ester, described catalyzer comprises alkali cpd and tin compound, and described initiator comprises diol compound.In addition, USP 4528364 (Date to Tender Notice of Readiness: 1984.04.19) discloses a kind of method removing catalyzer from prepared polymer compound.Therefore, the polymkeric substance produced has the carbon dioxide content being less than 30%, and is not alternating copolymer completely.In addition, use and prepare urethane be disclosed in Journal ofApplied Polymer Science, in 1990,41,487-507 by (alkylene carbonates) glycol that gathers of aforesaid method preparation and purifying.
EP 0222453 (Date to Tender Notice of Readiness: 1986.06.11) discloses a kind of passing through under the double metal cyanide as catalyzer exists, uses the organic materials with reactive proton as chain-transfer agent, carbonic acid gas and epoxide copolymerization to be synthesized the method for polyvalent alcohol.But the polyvalent alcohol obtained has the carbon dioxide content of 5 % by mole ~ 13 % by mole, and it not pure poly-(alkylene carbonates) compound of the complete alternating copolymerization based on carbonic acid gas and epoxide.
The CN 1060299A (Date to Tender Notice of Readiness: 1991.09.19) announced afterwards discloses under a kind of bimetallic catalyst by carrying at polymkeric substance exists and uses the organic materials with 1 ~ 10 reactive proton as chain-transfer agent to be prepared by carbonic acid gas and epoxide copolymerization the method for polyvalent alcohol.But thus obtained polyvalent alcohol has the carbon dioxide content of 37 % by mole ~ 40 % by mole, because of instead of pure poly-(alkylene carbonates) compound of complete alternating copolymerization based on carbonic acid gas and epoxide.
Synthesize lower molecular weight poly-(alkylene carbonates) about utilizing the alternating copolymerization of carbonic acid gas and epoxide and there is many reports.Carbonic acid gas and the copolymerization of epoxide are active or active (immortal) is polymerized forever, and wherein polymer chain is grown by the chain priming site of catalyzer.Therefore, when the activity of catalyzer is low, obtain low-molecular weight polymer.Except the catalyzer that the present inventor as above develops, most of catalyzer has low activity, produces and has 50, low-molecular-weight poly-(alkylene carbonates) of less than 000.But use has SA catalyst preparing lower molecular weight poly-(alkylene carbonates) needs a large amount of catalyzer, can not obtain economic return.In addition, because the chain priming site of polymer chain from catalyzer grows along a direction, therefore one end of chain has the chain priming site of catalyzer, and its other end Ju You – OH.Usually, the chain priming site comprised in the catalyst is alkoxyl group, aryloxy, carboxyl or halogenide.When polymer chain has this shape, namely make it have lower molecular weight, can not for the preparation of urethane.
Summary of the invention
Technical problem
Therefore, the present invention keeps the problem run in background technology firmly in mind, and the present invention aims to provide high activated catalyst that a kind of use developed to prepare the lower molecular weight poly-(alkylene carbonates) with molecular weight and the Similarity Between Line Segments accurately controlled to make carbonic acid gas and the complete alternating polymerization of epoxide method by adding chain-transfer agent, and provides use aforesaid method to prepare pure to gather (alkylene carbonates) compound.
The present invention also aims to provide a kind of pure poly-(alkylene carbonates), described pure poly-(alkylene carbonates) can be used alone in the multiple application comprising coating agent etc., or can react also thus for the preparation of urethane with isocyanate compound.
The technical scheme of dealing with problems
Embodiments of the present invention will be described in detail below.
The invention provides the method that one prepares poly-(alkylene carbonates), described method comprises use by the complex compound represented using following formula 1 as catalyzer, under the existence by the compound represented with following formula 5, by carbonic acid gas and one or more epoxy compounds alternating copolymerizations be selected from the group that is made up of following material: replace (C2-C20) alkylene oxide having or do not replace and have halogen, (C1-C20) alkoxyl group, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) alkoxyl group; Replace and have or do not replace (C4-C20) cycloalkylidene oxide compound having halogen, (C1-C20) alkoxyl group, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) alkoxyl group; Have with replacement or do not replace (C8-C20) styrene oxide having halogen, (C1-C20) alkoxyl group, (C6-C20) aryloxy, (C6-C20) aryl (C1-C20) alkoxyl group or (C1-C20) alkyl.
[formula 1]
In formula 1, M is trivalent cobalt or trivalent chromium;
A is oxygen or sulphur atom;
Q is the bivalent free radical of connection two nitrogen-atoms;
R
1~ R
10be hydrogen independently of one another; Halogen; (C1-C20) alkyl; (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C2-C20) thiazolinyl; (C2-C20) thiazolinyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkoxyl group; (C6-C30) aryloxy; Formyl radical; (C1-C20) alkyl-carbonyl; (C6-C20) aryl carbonyl; Or replace the metalloid radicals having the 14th race's metal of alkyl;
R
1~ R
10in two formation rings that can be connected to each other;
Be included in R
1~ R
10the proton group (proton group) being selected from formula a as follows, formula b and formula c with at least one hydrogen in Q:
[formula A]
[formula B]
[formula c]
X
-be halide anion independently; HCO
3 -; BF
4 -; ClO
4 -; NO
3 -; PF
6 -; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkyl carboxyl negatively charged ion; (C1-C20) alkyl carboxyl negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) aryl carboxy group negatively charged ion; (C6-C20) aryl carboxy group negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylcarbonate negatively charged ion; (C1-C20) alkylcarbonate negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylcarbonic acid root negatively charged ion; (C6-C20) arylcarbonic acid root negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylamino (alkylamido) negatively charged ion; (C1-C20) alkylamino negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylamino (arylamido) negatively charged ion; (C6-C20) arylamino negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylamino formate anion; (C1-C20) alkylamino formate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylamino formate anion; Or (C6-C20) arylamino formate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom;
Z is nitrogen or phosphorus atom;
R
21, R
22, R
23, R
31, R
32, R
33, R
34and R
35represent (C1-C20) alkyl independently of one another; (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C2-C20) thiazolinyl; (C2-C20) thiazolinyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; Or replace the metalloid radicals having the 14th race's metal of alkyl; R
21, R
22and R
23in two or R
31, R
32, R
33, R
34and R
35in two formation rings that can be connected to each other;
R
41, R
42and R
43be hydrogen independently of one another; (C1-C20) alkyl; (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C2-C20) thiazolinyl; (C2-C20) thiazolinyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; Or replace the metalloid radicals having the 14th race's metal of alkyl; R
41, R
42and R
43in two formation rings that can be connected to each other;
X ' is Sauerstoffatom, sulphur atom or N-R (wherein R is (C1-C20) alkyl);
N is to being included in R
1~ R
10the integer of 1 and acquisition is added with the sum of the proton group in Q;
X
-can with M coordination; And
The nitrogen-atoms of imines can with M deallocation position (decoordinated).
[formula 5]
J(LH)
c
In formula 5, J is the C1-C60 alkyl c valency free radical or do not have with ether, ester group or amino; LH is-OH or-CO
2h; And c is the integer of 1 ~ 10, wherein when c is more than 2, LH can be identical or different.
The compound represented by formula 1 is used to be obtained patent by the present inventor as the carbonic acid gas of catalyzer and the copolymerization of epoxide and be distributed on (Korean patent No. 10-0853358 in periodical; J.Am.Chem.Soc.2007,129,8082-8083; Angew.Chem.Int.Ed., 2008,47,7306-7309), but the compound that represented by formula 5 of use according to the present invention as the carbonic acid gas of chain-transfer agent and the copolymerization of epoxide not yet known.The process of growth of the polymer chain that what following scheme 1 showed is under chain-transfer agent exists.The copolymerization of carbonic acid gas and epoxide is by the X to formula 1 type catalyzer
-carry out nucleophillic attack to cause to make epoxide and serve as lewis acidic metal-complexing.When polyreaction is initiated, polymer chain starts the X by catalyzer
-growth, finally, X
-become the polymer chain that its end group is carbonate or alkoxy anion.Carbonate or alkoxy anion and the J (LH) represented by formula 5 added as chain-transfer agent
cthe proton of compound is converted into the compound of alcohol or carboxylic acid form together, and J (LH)
ccompound will become carboxyl or alkoxy anion.As J (LH)
cwhen compound becomes carboxyl or alkoxy anion, polymer chain can be grown by it.Proton-exchange reaction can very rapidly occur.React by proton exchange and chain growth the polymer materials obtained to comprise by the X of catalyzer
-growth polymer chain and by the J added as chain-transfer agent (LH)
cthe polymer chain of compound growth.The molecular weight of the polymkeric substance obtained and Similarity Between Line Segments can adjust according to the amount of added chain-transfer agent and structure.
[scheme 1]
(note: " Rapid Proton-Exchange and Chain-Growing " is " rapidly proton exchange and chain growth ")
Preferably, in formula 1, M is trivalent cobalt; A is oxygen;
Q is anti-form-1,2-cyclohexylidene, phenylene or ethylidene; R
1and R
2be identical or different, and be (C1-C20) primary alkyl; R
3~ R
10represent hydrogen or-[YR independently of one another
51 3-a{ (CR
52r
53)
bn
+r
54r
55r
56}
a]; Y is C or Si; R
51, R
52, R
53, R
54, R
55and R
56be hydrogen independently of one another; Halogen; (C1-C20) alkyl; (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C2-C20) thiazolinyl; (C2-C20) thiazolinyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkoxyl group; (C6-C30) aryloxy; Formyl radical; (C1-C20) alkyl-carbonyl; (C6-C20) aryl carbonyl; Or replace the metalloid radicals having the 14th race's metal of alkyl, R
54, R
55and R
56in two formation rings that are connected to each other; A is the integer of 1 ~ 3; And b is the integer of 1 ~ 20; N is for by being included in R
3~ R
10in the sum of quaternary ammonium salt add the integer of more than 4 of 1 acquisition, condition uses following complex compound as catalyzer, in described complex compound, the R when a is 1
3~ R
10in at least three be-[YR
51 3-a{ (CR
52r
53)
bn
+r
54r
55r
56}
a], the R when a is 2
3~ R
10in at least two be-[YR
51 3-a{ (CR
52r
53)
bn
+r
54r
55r
56}
a], or when a is 3 R
3~ R
10in at least one be-[YR
51 3-a{ (CR
52r
53)
bn
+r
54r
55r
56}
a].
Specifically, use by the complex compound represented with following formula 6 as above catalyzer.
[formula 6]
In formula 6, Q is anti-form-1,2-cyclohexylidene, phenylene or ethylidene;
R
1and R
2be identical or different, and be (C1-C20) primary alkyl;
R
3~ R
10be hydrogen or-[YR independently of one another
51 3-a{ (CR
52r
53)
bn
+r
54r
55r
56}
a];
Y is C or Si;
R
51, R
52, R
53, R
54, R
55and R
56be hydrogen independently of one another; Halogen; (C1-C20) alkyl; (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C2-C20) thiazolinyl; (C2-C20) thiazolinyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkoxyl group; (C6-C30) aryloxy; Formyl radical; (C1-C20) alkyl-carbonyl; (C6-C20) aryl carbonyl; Or replace the metalloid radicals having the 14th race's metal of alkyl, R
54, R
55and R
56in two formation rings that are connected to each other;
A is the integer of 1 ~ 3, and b is the integer of 1 ~ 20;
X
-be halide anion independently; HCO
3 -; BF
4 -; ClO
4 -; NO
3 -; PF
6 -; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkyl carboxyl negatively charged ion; (C1-C20) alkyl carboxyl negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) aryl carboxy group negatively charged ion; (C6-C20) aryl carboxy group negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylcarbonate negatively charged ion; (C1-C20) alkylcarbonate negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylcarbonic acid root negatively charged ion; (C6-C20) arylcarbonic acid root negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylamino negatively charged ion; (C1-C20) alkylamino negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylamino negatively charged ion; (C6-C20) arylamino negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylamino formate anion; (C1-C20) alkylamino formate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylamino formate anion; Or (C6-C20) arylamino formate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom;
Be included in R
3~ R
10in quaternary ammonium salt add up to more than 3 integer; And
N is to being included in R
3~ R
10in the sum of quaternary ammonium salt add 1 and obtain more than 4 integer.
R in formula 6
1and R
2for primary alkyl and the number being included in the quaternary ammonium salt in this compound is more than 3 time, it is known that, the unique coordination body of the non-coordination of nitrogen of the imines of wherein structure 1 is defined in polyreaction, and the high reactivity (Inorg.Chem.2009 shown especially thus in the copolymerization of carbonic acid gas and epoxide, 48,10455 – 10465; Bulletin of Korean Chemical Society 2010,31,829-834; Korean Patent Application No. 10-2008-0074435 (2008.07.30)).But the copolymerization using the compound represented by formula 5 to carry out carbonic acid gas and epoxide as chain-transfer agent under this catalyzer exists is but not yet known.
It is further preferred that use as above catalyzer the complex compound represented with following formula 7.
[formula 7]
In formula 7, R
61and R
62be methyl or ethyl independently of one another; N is the integer of 1 ~ 20; X
-be nitrate radical or acetic acid anion independently; The nitrogen of imines can with cobalt coordination or from cobalt deallocation position, and each negatively charged ion can with cobalt coordination.
Can easily to produce in a large number and the complex compound represented by formula 7 is very preferably known (the Bull.Korean Chem.Soc.2009 of the present inventor therefore and in commercialization, 30,745-748), but the copolymerization using the compound represented by formula 5 to carry out carbonic acid gas and epoxide as chain-transfer agent is in the presence of the catalyst unknown.
In the compound represented by formula 5, wherein c can be used to be 1; And J is that the compound of the C1-C60 alkyl radical or do not have with ether, ester group or amino is as chain-transfer agent.
Or in the compound represented by formula 5, wherein c can be used to be 2; And J be the compound of the C1-C60 alkyl bivalent free radical or do not have with ether, ester group or amino as chain-transfer agent, specifically, it can be selected from: the structure of the compound wherein represented by formula 5 is J (CO
2h)
2(J is-[CR
2]
n-(n is the integer of 0 ~ 20; R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl), to phenylene, metaphenylene, adjacent phenylene or 2,6-naphthalene two base) compound, the structure of the compound wherein represented by formula 5 is J (OH)
2(J is-[CR
2]
n-(n is the integer of 0 ~ 20; R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl) ,-CH
2cH
2n (R) CH
2cH
2-(R is C 1-C20 alkyl) or-[CH
2cH (R) O]
ncH
2cH (R)-(n is the integer of 0 ~ 10; And R is hydrogen or methyl)) compound, and the structure of the compound wherein represented by formula 5 is HO-C
6h
4-CO
2the compound of H.
Or in the compound represented by formula 5, wherein c can be used to be 3; And J is that the compound of the C1-C60 alkyl trivalent free radical or do not have with ether, ester group or amino is as chain-transfer agent.Specifically, the structure that there is the compound wherein represented by formula 5 is J (CO
2h)
3the compound of (J is 1,2,3-glyceryl, 1,2,3-benzene three base, 1,2,4-benzene three base or 1,3,5-benzene three base).
Or in the compound represented by formula 5, wherein c can be used to be 4; And J is that the compound of the C1-C60 alkyl tetravalence free radical or do not have with ether, ester group or amino is as chain-transfer agent.Specifically, the structure that there is the compound wherein represented by formula 5 is J (CO
2h)
4the compound of (J is 1,2,3,4-fourth four base or 1,2,4,5-benzene four base).
The specific examples of the epoxy compounds in preparation in accordance with the present invention comprises ethylene oxide, propylene oxide, oxybutylene, pentylene oxide, oxidation hexene, octylene oxide, decene oxide, oxidation laurylene, oxidation tetradecene, oxidation hexadecylene, oxidation octadecylene, butadiene monoxide, 1,2-epoxy-7-octene, epifluorohydrin, epoxy chloropropane, epoxy bromopropane, isopropyl glycidyl ether, butylglycidyl ether, tertiary butyl glycidyl ether, 2-hexyl glycidyl ether, glycidyl allyl ether, cyclopentene oxide, cyclohexene oxide, oxidation cyclooctene, oxidation cyclododecene, a-pinne oxide, 2,3-epoxynorborn alkene, limonene oxide, Dieldrin-attapulgite mixture (dieldrin), 2,3-epoxypropyl benzene, Styrene oxide 98min., oxidation phenylpropen, oxidation stilbene, chlorine monoxide stilbene, dichlorine monoxide stilbene, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxyethane, glycidyl-methyl phenyl ether, chloro-phenyl--2,3-glycidyl ethers, epoxypropyl p-methoxy-phenyl ether, biphenylyl glycidyl ether and glycidyl naphthyl ether.
Epoxy compounds can be used for an organic solvent as in the polymerization of reaction medium, and the example of solvent comprises aliphatic hydrocarbon, as pentane, octane, decane and hexanaphthene; Aromatic hydrocarbon, as benzene, toluene and dimethylbenzene; And halohydrocarbon, as methyl chloride, methylene dichloride, chloroform, tetracol phenixin, 1,1-ethylene dichloride, 1,2-ethylene dichloride, monochloroethane, trichloroethane, n-propyl chloride, 2 cbloropropane isopropyl chloride, 1-chlorobutane, Sec-Butyl Chloride, 1-chloro-2-methyl propane, chlorobenzene and bromobenzene, these solvents can be used alone or are used in combination with it.It is further preferred that the mass polymerization utilizing monomer self as solvent can be carried out.
The mol ratio of epoxide and catalyzer can be 1,000 ~ 1, and 000,000 is preferably 50,000 ~ 200,000.When copolymerization, pressure carbon dioxide can be barometric point ~ 100 normal atmosphere, is preferably 5 normal atmosphere ~ 30 normal atmosphere.In addition, polymerization temperature can be 20 DEG C ~ 120 DEG C, is preferably 50 DEG C ~ 90 DEG C.
Intermittent type, semibatch or successive polymerization can be adopted to be polymerized poly-(alkylene carbonates).When adopting intermittent type or semibatch polymerization, the reaction times can be set as 0.5 hour ~ 24 hours, preferably 0.5 hour ~ 4 hours.On the other hand, when adopting successive polymerization, the average retention time of catalyzer also can be set to 0.5 hour ~ 4 hours.
According to another embodiment of the present invention, the method for preparation poly-(alkylene carbonates) comprises and utilizes above-mentioned preparation section to prepare poly-(alkylene carbonates); With by the solution comprising the multipolymer prepared by being dissolved in wherein and catalyzer be insoluble to the solid mineral material of this solution, solid polymeric material or its mixture and contact, thus form the matrix material of solid mineral material or polymer materials and catalyzer, make thus multipolymer and catalyzer separated from one another.
Use identical catalyzer by carbonic acid gas and epoxide copolymerization then separating catalyst be known (the Korean patent No. 10-2008-0015454 of the present inventor; Angew.Chem.Int.Ed., 2008,47,7306-7309), but use the compound that represented by formula 5 as the copolymerization of chain-transfer agent and separating catalyst is not yet known afterwards.
Solid mineral material can be through or without the silicon-dioxide of surface modification or aluminium, and polymer materials can be have the polymer materials that can be caused the functional group of deprotonation by alkoxy anion, wherein the functional group of deprotonation can be caused can to comprise sulfonic acid group, hydroxy-acid group, phenolic groups or alcohol groups by alkoxy anion.
The specific examples of the solid mineral material formed primarily of the silicon or aluminium (described Brnsted acid position can be played and be proposed protogenic effect to alkoxy anion or carbonate anion) with Brnsted acid (bronsted acid) position comprises silicon-dioxide, aluminum oxide, aluminosilicate (zeolite), aluminate or phosphate, titanium silicate and clay.Useful especiallyly to be through or without surface-treated silicon-dioxide or aluminum oxide.
It is 500 ~ 10,000 that solid polymeric material is preferably number-average molecular weight, the crosslinked material of 000, even and if polymer materials also can use, as long as it is insoluble to the solution comprising multipolymer and catalyzer when crosslinked.Have and the specific examples of the solid polymeric material of the group of deprotonation can be caused to comprise the multipolymer comprising polymer chain by alkoxy anion, described polymer chain comprises by the monomer represented with following formula A ~ E, or the homopolymer be made up of this monomer separately.As the solid polymeric material of serving as this support, any not crosslinked material can be used, as long as it is insoluble to above-mentioned solution.But, preferably, use suitably crosslinked polymer materials to reduce solvability.
[formula A]
[formula B]
[formula C]
[formula D]
[formula E]
According to another embodiment of the present invention, provide by poly-(alkylene carbonates) that represent with following formula 10.
[formula 10]
J[L-{CR
81R
82-CR
83R
84-OC(O)O}
d-CR
81R
82-CR
83R
84-OH]
c
In formula 10, L is-O-or-CO
2-;
C is the integer of 2 ~ 10, and L is identical or different;
J is the C1-C60 alkyl c valency free radical or do not have with ether, ester group or amino;
R
81~ R
84be hydrogen independently of one another; Replace and have or do not replace (C1-C10) alkyl having halogen or (C1-C20) alkoxyl group; Replace and have or do not replace (C6-C12) aryl having halogen or (C1-C20) alkoxyl group; R
81~ R
84be connected to each other formation ring; And
D be multiplied by c obtain value be less than 1000 natural number.
As described in the background art, the structure of the polymer compound that the formula 10 being 1 by wherein c represents is identical with the structure of poly-(alkylene carbonates) that use conventional low activity catalyst to prepare, therefore can not prescription.But, wherein c be more than 2 polymer compound be considered to novel.As mentioned in the background, in order to prepare urethane by glycol or polymerization compounds, carbonic acid gas and epoxide copolymerization synthesize as initiator or chain-transfer agent by using the organic materials with reactive proton by described glycol or polyhydric alcohol polymer series of compounds, have paid many effort (USP 4686276; EP 0222453; CN 1060299A).But, this conventional catalyst has the activity and performance that are markedly inferior to catalyst according to the invention, and be unsuitable for commercial applications, and particularly cannot realize the complete alternating copolymerization of carbonic acid gas and epoxide, generating portion or almost all only comprise ehter bond and the polymer compound of not carbonate-containing key.On the contrary, catalyst according to the invention can realize the complete alternating copolymerization of carbonic acid gas and epoxide, obtains pure poly-(alkylene carbonates).
The maximum turnover number (turnover number, TON) obtained by catalyst according to the invention is about 20000.Polymer chain is by the X of catalyzer
-with the J (LH) of chain-transfer agent
cgrowth.The catalyzer with the structure represented by formula 7 has five X
-.When using this catalyzer to perform preparation in accordance with the present invention, exist by least five X
-the polymer chain (see scheme 1) of growth.At the J added as chain-transfer agent (LH)
cthe quantity of-LH functional group be equal to or greater than in the situation of 15 with the ratio of the quantity of catalyst molecule, by J (LH)
cthe amount of the polymer chain of growth constitutes and comprises by X
-growth polymer chain polymkeric substance total amount more than 75%.Therefore, in formula 8, d is multiplied by the value that c obtains and is set to less than 1000.When d be multiplied by value that c obtains for 1000 and the TON obtained in copolyreaction is 20000 time, as the J (LH) that chain-transfer agent adds
cthe quantity of-LH functional group and the ratio of the quantity of catalyst molecule be 15 times of the quantity of catalyst molecule.The chain-transfer agent J (LH) passing through obtained TON and add
camount determine the minimum value that d is multiplied by c and obtains.Due to for minimum TON and the chain-transfer agent J (LH) that adds
cmaximum there is not restriction, to be therefore multiplied by the minimum value that c obtains unrestricted for d.D is multiplied by the value that c obtains and can uses NMR spectrum analysis to measure when molecular weight is enough low, and can utilize the universal calibration of GPC to measure when molecular weight height.
When using batch reactor to be polymerized, the molecular weight distribution of polymkeric substance obtained according to the present invention is rather narrow (M
w/ M
n<1.2).But when using flow reactor, depend on that catalyst residence time distributes, molecular weight distribution can broaden, be therefore not limited to the numerical value using batch reactor to obtain.
Can coating material be used alone as according to poly-(alkylene carbonates) polymkeric substance of lower molecular weight that the present invention obtains, and also can use with other polymer blendings.In addition, utilize its-OH end group, this polymkeric substance may be used for preparing urethane.
In addition, the polymer compound represented by formula 10 can be following compound, and wherein, c is 2; J is the C1-C60 alkyl bivalent free radical or do not have with ether, ester group or amino; R
81~ R
84be hydrogen or methyl independently of one another; D is the integer of 5 ~ 500, preferred R
81~ R
84be all hydrogen, or R
81~ R
83all can be hydrogen and R
84can be methyl (in some repeating unit, R
81can be methyl and R
82~ R
84can be all hydrogen).
In addition, the polymer compound represented by formula 10 can be following compound, and wherein, c is 2; L is-CO
2-; And J is-[CR
2]
n-(n is the integer of 0 ~ 20; R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl), to phenylene, metaphenylene, adjacent phenylene or 2,6-naphthalene two base, or following compound, wherein, c is 2; L is-O-; And J is-[CR
2]
n-(n is the integer of 0 ~ 20; R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl) ,-CH
2cH
2n (R) CH
2cH
2-(R is C1-C20 alkyl) or-[CH
2cH (R) O]
ncH
2cH (R)-(n is the integer of 0 ~ 10; And R is hydrogen or methyl).
In addition, the polymer compound represented by formula 10 can be following compound, and wherein, c is 3; J is the C1-C60 alkyl trivalent free radical or do not have with ether, ester group or amino; R
81~ R
84be hydrogen or methyl independently of one another; And d is the natural number of less than 330, and preferred R
81~ R
84be all hydrogen, or R
81~ R
83all can be hydrogen and R
84can be methyl (in some repeating unit, R
81can be methyl and R
82~ R
84can be all hydrogen).
In addition, the polymer compound represented by formula 10 can be following compound, and wherein, c is 3; L is-CO
2-; And J is 1,2,3-glyceryl, 1,2,3-benzene three base, 1,2,4-benzene three base or 1,3,5-benzene three base.
In addition, the polymer compound represented by formula 10 can be following compound, and wherein, c is 4; J is the C1-C60 alkyl tetravalence free radical or do not have with ether, ester group or amino; R
81~ R
84be hydrogen or methyl independently of one another; D is the natural number of less than 250, and preferred R
81~ R
84be all hydrogen, or R
81~ R
83all can be hydrogen and R
84can be methyl (in some repeating unit, R
81can be methyl and R
82~ R
84can be all hydrogen).
In addition, the polymer compound represented by formula 10 can be following compound, and wherein, c is 4; L is-CO
2-; And J is 1,2,3,4-fourth four base or 1,2,4,5-benzene four base.
Be 3 or 4 using wherein c thus formed there are three or four branches starlike polymkeric substance in the situation preparing urethane, can cause crosslinked, can be used in the preparation of heat-curable urethane thus.
As noted before, the present invention provides the accurate control to molecular weight and Similarity Between Line Segments when carrying out the alternating copolymerization of carbonic acid gas and epoxide, and provides the preparation of lower molecular weight poly-(alkylene carbonates) thus.According to the present invention, chain-transfer agent is added in the copolymerization of carbonic acid gas and epoxide, can prepare thus poly-(alkylene carbonates), depend on amount and the shape of chain-transfer agent in this poly-(alkylene carbonates), molecular weight and polymer chain shape precisely controlled.Polymkeric substance precisely controlled thus provides the method for the molecular weight and molecualr weight distribution accurately controlling poly-(alkylene carbonates), thus makes the independent application variation gathering (alkylene carbonates).In addition, the polymkeric substance using aforesaid method to prepare has alcohol end group, therefore can easily for the preparation of urethane.
Accompanying drawing explanation
By the following detailed description together provided with accompanying drawing, the features and advantages of the present invention will obtain understanding clearly, wherein:
Fig. 1 display be the polymer compound that the hexanodioic acid of use 300 equivalent obtains as chain-transfer agent
1hNMR composes, and wherein, near 3.5ppm, no signal shows to achieve complete alternating copolymerization, and integrated value represents the chain-transfer agent of all interpolations participating in chain growth;
What Fig. 2 showed is the change of molecular weight and the narrow molecular weight distributions that depend on the amount of added hexanodioic acid and the polymkeric substance obtained of polymerization time, and the numeral wherein directly over each curve refers to the item number of table 1; With
What Fig. 3 showed is use polystyrene as standard substance by the relation between the molecular weight of gpc measurement and the absolute molecular weight calculated by turnover number (TON).
Embodiment
By the following embodiment that will illustrate, by acquisition to better understanding of the present invention, but should not think that these embodiments limit the present invention.
The synthesis of [preparation example 1] catalyzer
Catalyst according to the invention is prepared as shown below.Use currently known methods synthesis as the compd A (Bull.Korean Chem.Soc.2009,30,745-748) of raw material.
The synthesis of compd B
By compd A (100mg, 0.054mmol) and AgNO
3(37.3mg, 0.219mmol) is dissolved in ethanol (3mL), then stirs and spends the night.Use the solution that diatomite filtration stirs, and the AgI that removing generates.Utilize vacuum decompression to remove desolventizing, obtain yellow solid powdered compounds B (0.80g, 94%) thus.
1h NMR (CDCl
3): δ 3.51 (s, 2H, OH), 8.48 (s, 2H, CH=N), 7.15 (s, 4H, m-H), 3.44 (br, 2H, cyclohexyl-CH), 3.19 (br, 32H, NCH
2), 2.24 (s, 6H, CH
3), 1.57-1.52 (br, 4H, cyclohexyl-CH
2), 1.43-1.26 (br, 74H), 0.90-070. (br, 36H, CH
3) ppm.
The synthesis of Compound C
By compd B (95mg, 0.061mmol) and Co (OAc)
2(10.7mg, 0.061mmol) is placed in flask, then adds methylene dichloride (3mL) and makes it dissolve.Under oxygen in this solution of stirring at room temperature 3 hours, and decompression is with except desolventizing, obtains brown solid powdered compounds C (85mg, 83%).
1h NMR (DMSO-d
6, 38 DEG C): main signal group (major signal set), δ 7.83 (s, 2H, CH=N) 7.27 (br s, 2H, m-H), 7.22,7.19 (brs, 2H, m-H), 3.88 (br, 1H, cyclohexyl-CH), 3.55 (br, 1H, cyclohexyl-CH), 3.30-2.90 (br, 32H, NCH
2), 2.58 (s, 3H, CH
3), 2.55 (s, 3H, CH
3), 2.10-1.80 (br, 4H, cyclohexyl-CH
2), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH
3) ppm; Secondary signal group (minor signal set), δ 7.65 (s, 2H, CH=N) 7.45 (s, 2H, m-H), 7.35 (s, 2H, m-H), 3.60 (br, 2H, cyclohexyl-CH), 3.30-2.90 (br, 32H, NCH
2), 2.66 (s, 6H, CH
3), 2.10-1.80 (b r, 4H, cyclohexyl-CH
2), 1.70-1.15 (br m, 74H), 1.0-0.80 (br, 36H, CH
3) ppm.
1h NMR (CD
2cl
2): δ 7.65 (br, 2H, CH=N) 7.34 (br, 2H, m-H), 7.16 (br, 2H, m-H), 3.40-2.00 (br, 32H, NCH
2), 2.93 (br s, 6H, CH
3), 2.10-1.80 (br m, 4H, cyclohexyl-CH
2), 1.70-1.15 (br m, 74H), 1.1-0.80 (br, 36H, CH
3) ppm.
By Compound C is dissolved in DMSO-d
6middle acquisition
1during H NMR composes, the ratio of observing is two groups of signals of 6:4.Main signal group shows, two phenoxy ligands of Salen monomer are different, and secondary signal group shows, two phenoxy ligands are identical.This is considered to reason and is that Compound C is in the equilibrium state that will be described below in DMSO solvent.Verified, structure (the Inorg.Chem.2009 that the situation that the substituting group having little steric hindrance as methyl etc. is arranged in the ortho position of two phenoxy ligands of Salen monomer will cause the nitrogen of wherein imines in such as DMSO polar solvent not coordination, 48,10455 – 10465).Observe the signal of Dan Zufei constant width in as the methylene dichloride of non-polar solvent.Consider NO
3 -the weak coordination ability of negatively charged ion, estimation is following structure, and wherein, the nitrogen of imines by coordination, and coordination and deallocation position occurs at nitrate anion and acetic acid anion twin shaft coordinated planar is cocommutative simultaneously.
The structure > of the estimation of < Compound C in DMSO
< Compound C is at CH
2cl
2in the structure > of estimation
[embodiment 1] uses hexanodioic acid as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating copolymerization
By propylene oxide (10.0g, 172mmol) and preparation example 1 in obtain Compound C (3.0mg, monomer/catalyst=100,000) be added in 50mL bullet formula reactor (bomb reactor), and add hexanodioic acid with the amount of 10,25,50,75,100,200,300,400,500 of catalyzer mole number times as shown in Table 1 below, assemble this reactor afterwards.The Carbon dioxide air pressure of 15 bar is applied to this reactor, then by reactor leaching in the oil bath of 73 DEG C, stir afterwards.After 35 minutes, the internal temperature of reactor reaches 70 DEG C.From then on time point starts, and the pressure observing reactor reduces.Polymerization 1 hour (1st ~ 9), 30 minutes (the 10th) or 2 hours (the 11st) are carried out, initiation reaction thus the time point reaching 70 DEG C by the internal temperature of reactor.Reactor is immersed in cooling bath and cools thus, afterwards carbon dioxide gas, thus termination reaction, obtain thick pale yellow solution.
Catalyst separating
In this viscous solution, add 10g propylene oxide again to reduce soltion viscosity, make solution by silica gel (400mg, from Merck, 0.040 ~ 0.063mm particle diameter (230 order ~ 400 order)) pad afterwards, obtain colourless solution.Vacuum decompression is utilized to remove monomer.In some cases, about 1% ~ 10% propylene carbonate byproduct is produced.By removing propylene carbonate byproduct that sample storage is spent the night in the vacuum drying oven of 150 DEG C.Copolymerization the results are given in following table 1.Fig. 1 shows obtained polymkeric substance
1h NMR composes, and wherein near 3.5ppm, there is not signal, shows to achieve complete alternating copolymerization, and wherein integrated value shows that the chain-transfer agent of all interpolations take part in chain growth.Fig. 2 shows the change of molecular weight and the narrow molecular weight distributions of the polymkeric substance obtained of amount and the polymerization time depending on added hexanodioic acid.Numeral directly over each curve refers to the item number of table 1.
Table 1
Use hexanodioic acid as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent
Note: a: the molecular weight using polystyrene to measure as standard substance by GPC.B: the turnover number of the Mass Calculation of the polymkeric substance obtained after removing propylene carbonate byproduct by measurement.C: the molecular weight calculated by TON ([TON × 102.13]/[hexanodioic acid equivalent+5])
As can be obviously found out in table 1, the molecular weight of polymkeric substance can depend on the amount of added hexanodioic acid and precisely controlled.In addition, as as shown in table 1 and Fig. 2, except the situation (item number 1 and 2) that added hexanodioic acid equivalent is 10 and 25, the molecular weight distribution (Mw/Mn) of the polymkeric substance obtained is about 1.05, this is be evaluated as and is rather narrow, and polymer chain is growth by four nitrate anions of catalyzer C and an acetic acid anion.Nitrate anion and the acetic acid anion of growth become alkoxyl group or carbonate anion, and these negatively charged ion are combined by the proton of acid-base reaction with the hexanodioic acid added as chain-transfer agent.When during negatively charged ion is by proton and time, the growth of polymer chain stops.On the other hand, chain by occur deprotonation hexanodioic acid carboxyl anion growth.The acid-base reaction occurred by proton shifting is extremely rapid, and whole polymer chain is by the nitrate radical of catalyzer or acetic acid anion and the carboxyl homoepitaxial by the hexanodioic acid added as chain-transfer agent.Therefore, the polymer chain obtained by polymerization is the mixture comprising the polymer chain grown by nitrate radical or acetic acid anion and the polymer chain grown by hexanodioic acid.The polymkeric substance grown by hexanodioic acid is constructed to polymer chain is grown along both direction, and the polymkeric substance grown by nitrate radical or acetic acid anion is constructed to make polymer chain grow along a direction, its length is the half (following scheme 2) of the length of the chain grown by hexanodioic acid.As found out by Fig. 2, bimodal molecular weight distribution can be observed in the polymkeric substance of the item number 1 and 2 of table 1.It is considered to, and lower molecular weight peak is grown by nitrate radical or acetic acid anion, and high molecular weight peak is grown along both direction by hexanodioic acid.Amount due to added hexanodioic acid is significantly higher than the item number of item number 3 or higher, the quantity (more than 75) of the polymer chain therefore grown along both direction by hexanodioic acid is apparently higher than the quantity (5) of the polymer chain grown by nitrate radical or acetic acid anion, and the quantity of the polymer chain grown by acetic acid anion can be ignored.Therefore, see that the GPC curve of Fig. 2 is almost unimodal, and molecular weight distribution (Mw/Mn) is very little, in the level of about 1.05.
Use the end group of the chain of this catalyst growth for carbonate or alkoxy anion form, or be the carbonic acid with proton or alcohol form.When by obtained polymkeric substance by silicon-dioxide time, all carbonates or alkoxy anion can be converted into carbonic acid or alcohol together with proton.In the d/d atmosphere of carbonic acid gas, carbonic acid release of carbon dioxide, becomes alcohol thus.Specifically, in the end group of the polymer chain produced by catalyzer with removing by silicon-dioxide, the chain grown by chain-transfer agent has two end groups of dialcool form, and the chain grown by the nitrate radical of catalyzer or acetic acid anion comprises single methanol type chain, and described single methanol type chain has and comprises NO
3-or CH
3cO
2-an end group and comprise another end group of alcohol.What following scheme 2 showed is the polymer chain process of growth under chain-transfer agent exists.
[scheme 2]
(note: " Exchange and Chain-growing " is " exchanging and chain growth ";
" Proton Exchange and Chain-growing " is " proton exchange and chain growth ";
Polymerization and then Silica-filtration " be " polymerization, then silica filtration)
Along with the increase of the amount of added hexanodioic acid, obtain and there is low-molecular-weight polymkeric substance.In addition, to equal or far more than in the situation of the quantity of the nitrate radical of catalyzer or acetic acid anion, all polymkeric substance have narrow molecular weight distributions, think that polymer chain is grown by the hexanodioic acid of all interpolations thus in the amount of hexanodioic acid.Fig. 1's
1the integrated value of H NMR shows that polymer chain is grown by the hexanodioic acid of all interpolations.In this case, the molecular weight (Mn) of the polymkeric substance obtained can be calculated by the turnover number of polyreaction (TON).Specifically, TON is multiplied by 102.13 (they are the molecular weight of the repeating unit of alternating copolymer), then divided by the sum [hexanodioic acid equivalent+5 (quantity of nitrate radical and acetic acid anion)] of chain, the molecular weight (Mn) of polymkeric substance is obtained thus.In table 1, the molecular weight of calculating can be seen and be consistently different from each other by the molecular weight of gpc measurement.This difference be considered to owing to by during gpc measurement use polystyrene as standard substance.When by gpc measurement, although be most preferably used as poly-(propylene carbonate) of same polymer as standard substance, the sample as standard substance of poly-(propylene carbonate) cannot be bought.Use polystyrene (PS) as standard substance by the molecular weight of gpc measurement and by KM
a+1=K
(PS)m
(PS) a (PS)+1the absolute molecular weight of the sample represented is relevant.Therefore, M is the absolute molecular weight of poly-(propylene carbonate), K and a is Mark-Houwink (Mark-Houwink) constant of poly-(propylene carbonate), M
(PS)for using PS as the molecular weight of standard substance by gpc measurement, and K
(PS)with a (PS) Mark-Houwink constant that is PS.Above-mentioned relation is derived according to following hypothesis: identical with the hydrodynamic volume (Vh) of the PS standard substance be identified at this time point molecular weight by the hydrodynamic volume (Vh) of poly-(propylene carbonate) of GPC at any same time point.Hydrodynamic volume (Vh) is defined as KM
a+1/ 2.5A (A is avogadros constant).In above-mentioned relation, " KM
a+1=K
(PS)m
a (PS)+1" M=(K can be transformed to
(PS)/ K) M
(PS) (a (PS)+1)/(a+1).If polymer chain is grown by the hexanodioic acid of all interpolations as estimated, then the absolute molecular weight (M) of poly-(propylene carbonate) is identical with the molecular weight calculated by TON.As shown in Figure 3, the absolute molecular weight (M, y-axis value) calculated by TON and use PS are as the molecular weight (M of standard substance by gpc measurement
(PS), x-axis value) and be fit to M=0.263M
(PS) 1.09(R
2=0.995).GPC operational conditions (the THF solvent of poly-(propylene carbonate), 25 DEG C) under Mark-Houwink constant K and a can by the Mark-Houwink constant K of PS known under above-mentioned relation and GPC operational conditions (THF solvent, 25 DEG C)
(PS)(0.011mL/g) calculate with a (0.725).K and a calculated is respectively 0.041mL/g and 0.583.
[embodiment 2] uses ethanol as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it is that wherein c is 1 to use ethanol, LH is OH and J is the compound of the formula 5 of ethyl) replace hexanodioic acid as chain-transfer agent, and add with the amount of 600 of catalyzer mole number times or 1000 times, afterwards separating catalyst in an identical manner.When adding chain-transfer agent with 600 times, obtain 2.98g straight polymer, and the TON of this polymkeric substance being 16200, use PS standard substance to be 4500 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.05.When adding chain-transfer agent with 1000 times, obtain 1.56g straight polymer, and the TON of this polymkeric substance being 8500, use PS standard substance to be 1700 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.04.
1hNMR analyzes and shows that two kinds of samples are all complete alternating copolymers.
[embodiment 3] uses caproic acid as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it is that wherein c is 1 to use caproic acid, LH is COOH and J is the compound of the formula 5 of amyl group) replace hexanodioic acid as chain-transfer agent, and add with the amount of 600 of catalyzer mole number times, afterwards separating catalyst in an identical manner.Obtain 2.40g straight polymer, and the TON of this polymkeric substance is 13300, use PS standard substance to be 3800 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) is 1.06.
1h NMR analyzes and shows that this sample is complete alternating copolymer.
[embodiment 4] uses succsinic acid as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it 2, LH is COOH and J is – CH for wherein c to use succsinic acid
2cH
2-the compound of formula 5) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 300 of catalyzer mole number times, afterwards separating catalyst in an identical manner.Obtain 1.78g straight polymer, and the TON of this polymkeric substance is 9700, use PS standard substance to be 5500 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) is 1.04.
1h NMR analyzes and shows that this sample is complete alternating copolymer.
[embodiment 5] makes spent glycol as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it 2, LH is OH and J is – CH for wherein c to make spent glycol
2cH
2-the compound of formula 5) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 300 of catalyzer mole number times, afterwards separating catalyst in an identical manner.Obtain 1.71g straight polymer, and the TON of this polymkeric substance is 9300, use PS standard substance to be 5200 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) is 1.04.
1h NMR analyzes and shows that this sample is complete alternating copolymer.
[embodiment 6] uses Diethylene Glycol as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it 2, LH is OH and J is-CH for wherein c to use Diethylene Glycol
2cH
2oCH
2cH
2-the compound of formula 5) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 100 of catalyzer mole number times, 300 times or 500 times, afterwards separating catalyst in an identical manner.When adding chain-transfer agent with 100 times, obtain 2.42g straight polymer, and the TON of this polymkeric substance being 13500, use PS standard substance to be 19800 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.03.When adding chain-transfer agent with 300 times, obtain 1.62g straight polymer, and the TON of this polymkeric substance being 8900, use PS standard substance to be 5400 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.04.When adding chain-transfer agent with 500 times, obtain 1.12g straight polymer, and the TON of this polymkeric substance being 6700, use PS standard substance to be 2500 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.05.
1h NMR analyzes and shows that all samples is all complete alternating copolymer.
The present embodiment shows, ether can not cause preparation in accordance with the present invention to go wrong.
[embodiment 7] uses N-phenyldiethanol-amine as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it 2, LH is OH and J is-CH for wherein c to use N-phenyldiethanol-amine
2cH
2n (Ph) CH
2cH
2-the compound of formula 5) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 100 of catalyzer mole number times or 200 times, afterwards separating catalyst in an identical manner.When adding chain-transfer agent with 100 times, obtain 3.15g straight polymer, and the TON of this polymkeric substance being 17000, use PS standard substance to be 26400 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.05.When adding chain-transfer agent with 200 times, obtain 1.12g straight polymer, and the TON of this polymkeric substance being 6100, use PS standard substance to be 5300 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.06.
1h NMR analyzes and shows that two kinds of samples are all complete alternating copolymers.
The present embodiment shows, amino can not cause preparation in accordance with the present invention to go wrong.
[embodiment 8] uses 4-HBA as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it has one for-OH and another is CO for wherein c in 2, two LH to use 4-HBA
2h, and J is the compound of the formula 5 to phenylene) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 300 of catalyzer mole number times, afterwards separating catalyst in an identical manner.Obtain 2.00g straight polymer, and the TON of this polymkeric substance is 109000, use PS standard substance to be 6600 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) is 1.04.
1h NMR analyzes and shows that this sample is complete alternating copolymer.
[embodiment 9] uses 1,2,3-the third three acid as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it is CO for wherein c is 3, LH to use 1,2,3-the third three acid
2h and J are the compound of the formula 5 of 1,2,3-glyceryl) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 100 of catalyzer mole number times, 133 times or 200 times, afterwards separating catalyst in an identical manner.When adding chain-transfer agent with 100 times, obtain 2.40g straight polymer, and the TON of this polymkeric substance being 13000, use PS standard substance to be 18800 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.03.When adding chain-transfer agent with 133 times, obtain 1.42g straight polymer, and the TON of this polymkeric substance being 7700, use PS standard substance to be 8000 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.04.When adding chain-transfer agent with 200 times, obtain 1.49g straight polymer, and the TON of this polymkeric substance being 8100, use PS standard substance to be 6200 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) being 1.04.
1h NMR analyzes and shows that these three kinds of samples all are all complete alternating copolymers.
[embodiment 10] uses 1,2,4-benzene tricarboxylic acid (1,2,4-benzenetricarboxylic acid) as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it is that wherein c is 3, LH is-CO to use 1,2,4-benzene tricarboxylic acid
2h and J are the compound of the formula 5 of 1,2,4-benzene three base) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 200 of catalyzer mole number times, afterwards separating catalyst in an identical manner.Obtain 1.12g straight polymer, and the TON of this polymkeric substance is 6000, use PS standard substance to be 4500 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) is 1.05.
1h NMR analyzes and shows that this sample is complete alternating copolymer.
[embodiment 11] uses 1,2,3,4-fourth tetracid as the carbonic acid gas/propylene oxide copolymerization of chain-transfer agent and catalyst separating
Carry out polyreaction in the same manner as example 1, difference is, (it is that wherein c is 4, LH is-CO to use 1,2,3,4-fourth tetracid
2h and J are the compound of the formula 5 of 1,2,3,4-fourth four base) replace hexanodioic acid as chain-transfer agent, and to add with the amount of 150 of catalyzer mole number times, afterwards separating catalyst in an identical manner.Obtain 2.01g straight polymer, and the TON of this polymkeric substance is 9200, use PS standard substance to be 4200 by the molecular weight (Mn) of gpc measurement, and molecular weight distribution (Mw/Mn) is 1.03.
1h NMR analyzes and shows that this sample is complete alternating copolymer.
Although disclose embodiments of the present invention for illustration purposes, one skilled in the art will appreciate that and can carry out many difference amendments, interpolation and replace, and do not depart from scope and spirit of the present invention disclosed in claims.Therefore, described amendment, interpolation and replacement also should be considered to fall within the scope of the present invention.
Industrial applicibility
As noted before, the present invention provides the accurate control to molecular weight and Similarity Between Line Segments when carrying out the alternating copolymerization of carbonic acid gas and epoxide, and provides the preparation of lower molecular weight poly-(alkylene carbonates) thus.According to the present invention, chain-transfer agent is added in the copolymerization of carbonic acid gas and epoxide, can prepare thus poly-(alkylene carbonates), depend on amount and the shape of chain-transfer agent in this poly-(alkylene carbonates), molecular weight and polymer chain shape precisely controlled.Polymkeric substance precisely controlled thus provides the method for the molecular weight and molecualr weight distribution accurately controlling poly-(alkylene carbonates), thus makes the independent application variation gathering (alkylene carbonates).In addition, the polymkeric substance using aforesaid method to prepare has alcohol end group, therefore can easily for the preparation of urethane.
Claims (22)
1. prepare the method for poly-(alkylene carbonates) for one kind, described method comprises use by the complex compound represented using following formula 1 as catalyzer, under the existence by the compound represented with following formula 5, by carbonic acid gas and one or more epoxy compounds alternating copolymerizations be selected from the group that is made up of following material: replace (C2-C20) alkylene oxide having or do not replace and have halogen, (C1-C20) alkoxyl group, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) alkoxyl group; Replace and have or do not replace (C4-C20) cycloalkylidene oxide compound having halogen, (C1-C20) alkoxyl group, (C6-C20) aryloxy or (C6-C20) aryl (C1-C20) alkoxyl group; Have with replacement or do not replace (C8-C20) styrene oxide having halogen, (C1-C20) alkoxyl group, (C6-C20) aryloxy, (C6-C20) aryl (C1-C20) alkoxyl group or (C1-C20) alkyl, to prepare poly-(alkylene carbonates) multipolymer:
Contact comprising the solution being dissolved in described multipolymer wherein and catalyzer with the solid mineral material being insoluble to described solution, solid polymeric material or its mixture, form the matrix material of described solid mineral material or polymer materials and described catalyzer thus, thus make described multipolymer and described catalyzer separated from one another
[formula 1]
In formula 1, M is trivalent cobalt or trivalent chromium;
A is oxygen or sulphur atom;
Q is the bivalent free radical of connection two nitrogen-atoms;
R
1and R
2be hydrogen independently of one another; Halogen; (C1-C20) alkyl; (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C2-C20) thiazolinyl; (C2-C20) thiazolinyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkoxyl group; (C6-C30) aryloxy; Formyl radical; (C1-C20) alkyl-carbonyl; (C6-C20) aryl carbonyl; Or replace the metalloid radicals having the 14th race's metal of alkyl;
X
-be halide anion independently; HCO
3 -; BF
4 -; ClO
4 -; NO
3 -; PF
6 -; (C6-C20) aryloxy anion; (C6-C20) aryloxy anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkyl carboxyl negatively charged ion; (C1-C20) alkyl carboxyl negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) aryl carboxy group negatively charged ion; (C6-C20) aryl carboxy group negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkoxy anion; (C1-C20) alkoxy anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylcarbonate negatively charged ion; (C1-C20) alkylcarbonate negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylcarbonic acid root negatively charged ion; (C6-C20) arylcarbonic acid root negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylsulfonate anion; (C1-C20) alkylsulfonate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylamino negatively charged ion; (C1-C20) alkylamino negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylamino negatively charged ion; (C6-C20) arylamino negatively charged ion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C1-C20) alkylamino formate anion; (C1-C20) alkylamino formate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; (C6-C20) arylamino formate anion; Or (C6-C20) arylamino formate anion containing at least one be selected from halogen atom, nitrogen-atoms, Sauerstoffatom, Siliciumatom, sulphur atom and phosphorus atom; X
-in at least one be NO
3 -;
R
3~ R
10be hydrogen or-[YR independently of one another
51 3-a{ (CR
52r
53)
bn
+r
54r
55r
56}
a];
Y is C;
R
51for (C1-C20) alkyl;
R
52, R
53, R
54, R
55and R
56be hydrogen independently of one another; Halogen; (C1-C20) alkyl; (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C2-C20) thiazolinyl; (C2-C20) thiazolinyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkyl (C6-C20) aryl; (C1-C20) alkyl (C6-C20) aryl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C6-C20) aryl (C1-C20) alkyl; (C6-C20) aryl (C1-C20) alkyl containing at least one be selected from halogen, nitrogen, oxygen, silicon, sulphur and phosphorus; (C1-C20) alkoxyl group; (C6-C30) aryloxy; Formyl radical; (C1-C20) alkyl-carbonyl; (C6-C20) aryl carbonyl; Or replace the metalloid radicals having the 14th race's metal of alkyl, R
54, R
55and R
56in two formation rings that can be connected to each other;
A is the integer of 2, and b is the integer of 1 ~ 20; And
N is to being included in R
3~ R
10in the sum of quaternary ammonium salt add 1 and obtain more than 4 integer,
Condition is, R
3~ R
10in at least two be-[YR
51 3-a{ (CR
52r
53)
bn
+r
54r
55r
56}
a];
X
-can with M coordination; And
The nitrogen-atoms of imines can from M deallocation position;
[formula 5]
J(LH)
c
Wherein, J is the C1-C60 alkyl c valency free radical or do not have with ether, ester group or amino; LH is-OH or-CO
2h; And c is the integer of 1 ~ 10, and wherein when c is more than 2, LH is identical or different.
2. the method for claim 1, wherein M is trivalent cobalt;
A is oxygen;
Q is anti-form-1,2-cyclohexylidene, phenylene or ethylidene; With
R
1and R
2be identical or different, and be (C1-C20) primary alkyl.
3. method as claimed in claim 2, wherein, uses by the complex compound represented with following formula 7 as catalyzer:
[formula 7]
Wherein, R
61and R
62be methyl or ethyl independently of one another; X
-be nitrate radical or acetic acid anion independently, X
-in at least one be NO
3 -; The nitrogen of imines can with cobalt coordination or from cobalt deallocation position, each negatively charged ion can with cobalt coordination.
4., the method for claim 1, wherein in the compound represented by formula 5, c is 1; And J is the C1-C60 alkyl radical or do not have with ether, ester group or amino.
5., the method for claim 1, wherein in the compound represented by formula 5, c is 2; And J is the C1-C60 alkyl bivalent free radical or do not have with ether, ester group or amino.
6. method as claimed in claim 5, wherein, in the compound represented by formula 5, LH is-CO
2h; And J is-[CR
2]
n-, to phenylene, metaphenylene, adjacent phenylene or 2,6-naphthalene two base, described-[CR
2]
nmiddle n is the integer of 0 ~ 20; R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl.
7. method as claimed in claim 5, wherein, in the compound represented by formula 5, LH is-OH; And J is-[CR
2]
n-,-CH
2cH
2n (R) CH
2cH
2-or-[CH
2cH (R) O]
ncH
2cH (R)-, described-[CR
2]
n-middle n is the integer of 0 ~ 20, and R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl; Described-CH
2cH
2n (R) CH
2cH
2-middle R is C1-C20 alkyl; Described-[CH
2cH (R) O]
ncH
2cH (R)-middle n is the integer of 0 ~ 10; And R is hydrogen or methyl.
8. method as claimed in claim 5, wherein, in the compound represented by formula 5, the Ge in two LH is – OH, and another Wei – CO
2h, and J is phenylene.
9., the method for claim 1, wherein in the compound represented by formula 5, c is 3; And J is the C1-C60 alkyl trivalent free radical or do not have with ether, ester group or amino.
10. method as claimed in claim 9, wherein, in the compound represented by formula 5, LH is – CO
2h; And J is 1,2,3-glyceryl, 1,2,3-benzene three base, 1,2,4-benzene three base or 1,3,5-benzene three base.
11. the method for claim 1, wherein in the compound represented by formula 5, and c is 4; And J is the C1-C60 alkyl tetravalence free radical or do not have with ether, ester group or amino.
12. methods as claimed in claim 11, wherein, in the compound represented by formula 5, LH Wei – CO
2h; And J is 1,2,3,4-fourth four base or 1,2,4,5-benzene four base.
13. the method for claim 1, wherein, described solid mineral material be through or without the silicon-dioxide of surface modification or aluminum oxide, and described solid polymeric material is have the polymer materials that can be caused the functional group of deprotonation by alkoxy anion.
14. methods as claimed in claim 13, wherein, describedly can cause the functional group of deprotonation to be sulfonic acid group, hydroxy-acid group, phenolic groups or alcohol groups by alkoxy anion.
15. 1 kinds by poly-(alkylene carbonates) that represent with following formula 10:
[formula 10]
J[L-{CR
81R
82-CR
83R
84-OC(O)O}
d-CR
81R
82-CR
83R
84-OH]
c
Wherein, L is-O-or-CO
2-;
C is the integer of 2 ~ 10, and L is identical or different;
J is the C1-C60 alkyl c valency free radical or do not have with ether, ester group or amino;
R
81~ R
84be hydrogen independently of one another; Replace and have or do not replace (C1-C10) alkyl having halogen or (C1-C20) alkoxyl group; Or replace and have or do not replace (C6-C12) aryl having halogen or (C1-C20) alkoxyl group, R
81~ R
84can be connected to each other formation ring; And
D be multiplied by c obtain value be less than 1000 natural number.
16. as claimed in claim 15 poly-(alkylene carbonates), and wherein, c is 2; J is the C1-C60 alkyl bivalent free radical or do not have with ether, ester group or amino; R
81~ R
84be hydrogen or methyl independently of one another; And d is the natural number of less than 500.
17. as claimed in claim 16 poly-(alkylene carbonates), and wherein, L is-CO
2-; J is-[CR
2]
n-, to phenylene, metaphenylene, adjacent phenylene or 2,6-naphthalene two base; Described-[CR
2]
n-middle n is the integer of 0 ~ 20, and R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl.
18. as claimed in claim 16 poly-(alkylene carbonates), and wherein, L is-O-; And J is-[CR
2]
n-,-CH
2cH
2n (R) CH
2cH
2-or-[CH
2cH (R) O]
ncH
2cH (R)-; Described-[CR
2]
n-middle n is the integer of 0 ~ 20, and R is identical or different, and is hydrogen, methyl, ethyl, propyl group or butyl; Described-CH
2cH
2n (R) CH
2cH
2-middle R is C1-C20 alkyl, described-[CH
2cH (R) O]
ncH
2cH (R)-middle n is the integer of 0 ~ 10, and R is hydrogen or methyl.
19. as claimed in claim 15 poly-(alkylene carbonates), and wherein, c is 3; J is the C1-C60 alkyl trivalent free radical or do not have with ether, ester group or amino; R
81~ R
84be hydrogen or methyl independently of one another; And d is the natural number of less than 330.
20. as claimed in claim 19 poly-(alkylene carbonates), and wherein, L is-CO
2-; And J is 1,2,3-glyceryl, 1,2,3-benzene three base, 1,2,4-benzene three base or 1,3,5-benzene three base.
21. as claimed in claim 15 poly-(alkylene carbonates), and wherein, c is 4; J is the C1-C60 alkyl tetravalence free radical or do not have with ether, ester group or amino; R
81~ R
84be hydrogen or methyl independently of one another; And d is the natural number of less than 250.
22. as claimed in claim 21 poly-(alkylene carbonates), and wherein, L is-CO
2-; And J is 1,2,3,4-fourth four base or 1,2,4,5-benzene four base.
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|---|---|---|---|
| KR10-2010-0031457 | 2010-04-06 | ||
| KR1020100031457A KR101715657B1 (en) | 2010-04-06 | 2010-04-06 | Precise control of molecular weight and chain shape control in carbon dioxide/epoxide alternating copolymerization and preparation of low molecular weight poly(alkylene carbonate) thereby |
| PCT/KR2010/008120 WO2011126195A1 (en) | 2010-04-06 | 2010-11-17 | Precise control of molecular weight and chain shape in carbon dioxide/epoxide alternating copolymerization and preparation of low-molecular-weight poly(alkylene carbonate) thereby |
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| US (2) | US8530616B2 (en) |
| EP (1) | EP2556101A4 (en) |
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| KR (1) | KR101715657B1 (en) |
| CN (1) | CN102939319B (en) |
| BR (1) | BR112012025527A2 (en) |
| CA (1) | CA2795533A1 (en) |
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| KR101404702B1 (en) * | 2011-03-08 | 2014-06-17 | 에스케이이노베이션 주식회사 | Preparation method for carbon dioxide/epoxide copolymers containing ether linkages |
| US9403861B2 (en) * | 2011-12-11 | 2016-08-02 | Novomer, Inc. | Salen complexes with dianionic counterions |
| WO2013096602A1 (en) | 2011-12-20 | 2013-06-27 | Novomer, Inc. | Methods for polymer synthesis |
| EP2838954A4 (en) | 2012-04-16 | 2015-11-25 | Novomer Inc | Adhesive compositions and methods |
| ES2707301T3 (en) | 2012-05-24 | 2019-04-03 | Saudi Aramco Tech Co | Polymerization system for the copolymerization of CO2 and epoxides and related method |
| WO2014084559A1 (en) * | 2012-11-29 | 2014-06-05 | Sk Innovation Co.,Ltd. | Method for preparing polycarbonate |
| KR101975036B1 (en) | 2013-03-21 | 2019-05-03 | 에스케이이노베이션 주식회사 | Preparation of poly(alkylene carbonate) via carbon dioxide/epoxide copolymerization in the presence of novel complex |
| KR102105891B1 (en) | 2013-07-09 | 2020-05-04 | 에스케이이노베이션 주식회사 | novel complex and preparation of poly(alkylene carbonate) using the same |
| KR102220786B1 (en) * | 2013-07-18 | 2021-03-02 | 에스케이이노베이션 주식회사 | Double Metal Cyanide Catalyst and Epoxide/Carbon Dioxide Copolymer |
| CN103788360B (en) * | 2014-01-08 | 2016-01-06 | 华侨大学 | Combine lower molecular weight carbon dioxide copolymer of ring-opening polymerization and Click reaction and preparation method thereof |
| CN103772691B (en) * | 2014-01-08 | 2016-02-24 | 华侨大学 | Combine the preparation method of the lower molecular weight carbon dioxide copolymer of Click reaction and ATRP reaction |
| CN103772690B (en) * | 2014-01-08 | 2016-02-24 | 华侨大学 | Combine the preparation method of the lower molecular weight carbon dioxide copolymer of ring-opening polymerization and Click reaction |
| KR102184946B1 (en) * | 2014-11-03 | 2020-12-01 | 에스케이이노베이션 주식회사 | Terpolymerization of carbon dioxide, epoxide and cyclic anhydride |
| KR102094452B1 (en) * | 2015-09-21 | 2020-03-27 | 주식회사 엘지화학 | Preparation method of polyalkylene carbonate |
| KR102409995B1 (en) * | 2016-02-26 | 2022-06-15 | 에스케이이노베이션 주식회사 | method for producing a poly(alkylene carbonate)polyol |
| WO2019112930A1 (en) | 2017-12-06 | 2019-06-13 | Saudi Aramco Technologies Company | Adhesive compositions and methods |
| WO2019204553A1 (en) | 2018-04-18 | 2019-10-24 | Saudi Aramco Technologies Company | End-group isomerization of poly(alkylene carbonate) polymers |
| US11180609B2 (en) | 2018-08-02 | 2021-11-23 | Saudi Aramco Technologies Company | Sustainable polymer compositions and methods |
| US11634539B2 (en) | 2018-09-24 | 2023-04-25 | Saudi Aramco Technologies Company | Polycarbonate block copolymers and methods thereof |
| CN110628010B (en) * | 2019-10-18 | 2022-09-27 | 辽宁奥克医药辅料股份有限公司 | Catalyst composition and method for preparing polyethylene glycol with medium molecular weight by using same |
| JP2023514009A (en) * | 2019-12-17 | 2023-04-05 | ユニバーシティ、オブ、サウサンプトン | Compositions and methods |
| WO2021262845A1 (en) | 2020-06-24 | 2021-12-30 | Saudi Aramco Technologies Company | Polyol compositions and methods |
| WO2022153213A1 (en) | 2021-01-15 | 2022-07-21 | Saudi Aramco Technologies Company | Systems and methods for drying compounds |
| WO2022153234A1 (en) | 2021-01-15 | 2022-07-21 | Saudi Aramco Technologies Company | Polycarbonate polyol nanocomposites |
| EP4359460A1 (en) | 2021-06-23 | 2024-05-01 | Saudi Aramco Technologies Company | Polyol compositions and methods |
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| KR101715657B1 (en) | 2017-03-14 |
| EP2556101A4 (en) | 2015-11-11 |
| WO2011126195A1 (en) | 2011-10-13 |
| KR20110112061A (en) | 2011-10-12 |
| US8530616B2 (en) | 2013-09-10 |
| EP2556101A1 (en) | 2013-02-13 |
| US9023979B2 (en) | 2015-05-05 |
| CN102939319A (en) | 2013-02-20 |
| TW201134851A (en) | 2011-10-16 |
| BR112012025527A2 (en) | 2016-06-21 |
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